Polynitroamines



' polynitro amines. the condensation was conducted at a pH beIow abOut'S States atet his Patented Apr-{4, 1961 This invention relates to new compositions of matter and a method for their preparation. In particulan this invention relates to secondary polynitro amines having the general formula:

wherein A is an alkylene radical and R and R are'nitro or alkyl radicals, at least one R being alkyL- I y I This application is a continuation-in-part of our copending Uni-tedStates patent application Serial No. 419,615, filed March 29, 1954, now abandoned.

Due to their high oxygen content and stability, these compounds find valuable use/as explosives. They may also be incorporated .in resinous propellant fuels where they serve as oxygen donors or modifiers. v

The compounds of this invention are prepared by condensing B-geminal polynitro alcohols with ammonia or Optimum results were obtained when Y condensed in the manner describedin Example I to pro- I and preferably from about .4 to about 18. As a matter ofconvenience, the ammonia oramine'is -usually,pro.

duced in situ. I

' The unsymmetrical secondaryaminesvaregprepared :by

condensing the alcohol with-a polynitrotamine, asillusprimary amine is employed as a salt'ofia" strong mineral amines arei'prepared by condensing the -"alcoh'ol =withf 'ammonia as illustrated by the generalreaction-'echeme 'set acid yielding'the free amine in situ in'the presenceyof a hydroxide or weakor'ga'nic acid salt of an alkali-or alkaline earth metal; --'Alternativel-y,the amine may be introduced as a salt of a Weak organic acid which readily hydrolyzes producing the free amine.

Generally as a matter of'conveniencethe symmetrical tion are obtained by'condensing labile hydrogen containingjnitr'oalkanes with formaldehyde. The-amines; anetpre- -pared by reactin'g a strong mineral acid withqthe correas'sig'nees copending application No. 405,515, filed January 21, 1954, now U.S. Patent No."2,923,726.

To, more clearly illustrate this invention, the following examples are presented. It is to be understood, however, that these examples are presented'merel'y-as a means of illustration-and are not intended'to limit the scope of the invention in any way. a

EXAMPLE I Preparation 0]" N-3,3-dinitr0butyl- -2,2,2-

trinitroethyl amine To a solution of 30 gm. 0.15 mole) of 3,3-dinitrobutyl amine hydrochloride,.27 gm. (0.15 mole) of trinitroethanol and 1 00 ml. of water, was added 132ml. of 1.36 'N sodium hydroxide solution (0.15 mole). An oil was formed which was extracted with methylene chloride and subsequently concentrated to yield an amber liquid (71.7%). The explosive values for this compoundare:

Lead block value 138 TNT=100.. Ballistic mortar value 144 TNT =100.

EXAMPLE II Preparation of N-2,2-diniir0pr 0py[JV-3,33-

trinitropropyl amine 2,2-dinitropropanol and 3,3,3-trinitropropyl aminewere duce an amber oil in quantitative yield. The explosive values for this compound are: 8 Lead block value 138 TNT: 100.

V Ballistic mortar value 144 TNT -100.

" :EXAMPLE 111 p H Preparation of bis(2,2-dinitr0pr0pyl) amine A solution of 30 gm. (0.39 mole)-of ammonium acetate in 50 ml. of water was added to 30 gm. (0.020 mole.) of

2,2-dinitropropanol. The reaction was warmed on a' steambath for 20'minutes; On cooling 25.4 gm. (90.4%) of a cream-colored solid separated which upon recrystallization from methanol and Water exhibited a M.P. of

62-63" C. and an impact stability greater than 100- .cm./2 kg.

7 N02 wherein A is an ,allcyleneradical and R and R. aregalkyl or nitro radicals, at'least one R being 'alkyl. Usually thev I "EXAMPLEIV Preparation of bis(2,2-di nitroamyl)'amine 4' A quantity of 11. gm. of 2,2-dinitropentanol was warmed on a steambath for 20 minutes with a solution of 11.6 gm. of ammonium acetate in 100 ml. of water. On

cooling a solid precipitated. Recrystallization of the solid from ethanol yielded White rods, M.P. 100-1005 C.

The elemental analysis of the product is as follows:

. Calculated for C l-1 N 05: percentgC,35;6l; percent:H,

ample" IV and recrystallizin'g the product from-.isopropyl I alcohol inayield of 99%, M.P. 6646.7tC. The elemental p I analysis of "theproductis asfollow's zxf i wherein R is an, alkyl radical, An ammonium salt ofa. weak organic; acid is usuallyemployed as the ammonia donor. 4

I .The alcohols used as startingvmaterials for this inven- 5.68; percent N, g 20.77.. Found:

percent 0, 135178; Fpercent H, 5.58; percent;N,:19. 75..]-- p ",Ijpg;

' EXAMPLE V;

Preparation; bf bisQjZ dz'fiitr buZyZ) amine Bis(2,2-'dinitrobutyl) amine w s prepared from 2,2-di- V nitrohutanol by following the procedure describedinlE x- Calculated for'C H 'NgO percent C, H, 4.89; percent N,.2-2.65. Foundzpercent C, 31.06;percent H, 4.98; percent N, 21.73. 1

-We have also-found-"that amines such as '5,5",5-trinitro pentyl: amine, 4,4-dinit-ropentyl: -Fan1ine, 3,3-dinitro-4- methylpentyl amine, etc., readily condense with' firgeminal N-2,2-dinitro-3 mthylbutyl amine, N-5,5,5-trinitropentyl-' N 2,2 dinitro-3,3-dimethylbutyl amine, N-4,4-dinitro pentyl-N-2,2-dinitro-3-methylbutyl amine, N-4,4-dinitropentyl-N-2,2-dinitro-3,3-dimethylbutyl amine, N-3,3-dinitro-4-methylpentyl-N-2,2-dinitro-S-methylbutyl amine, and N 3,3- dinitro-4-methylpentyl-N-2,2-dinitro-3,3-dimethylbutyl amine.

It is apparent that any polynitro amine of this series can be prepared by merely selecting an appropriate amine and condensing it with a B-geminal dinitro alcohol, in accordance with the teachings of this invention.

The nitro compounds of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1 949. One Way of using the high explosives of this invention in a device such as that disclosed in United States. Patent No. 2,470,162 is to pack the crystallineexplosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejectionof a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The liquid explosive compositions of this, invention are preferably absorbed in cotton, sawdust or similar materials for use as explosives. This technique is the same as is employed in the manufacture of commercial dynamites, gun cotton and the like. The absorbed material presents considerably less hazard in this form and can still be used in the same manner as the solid or crystalline explosives of this invention.

We claim:

1. As compositions of matter, the secondary polynitro amines having the general formula:

wherein A is a lower alkylene radical and R and R are lower alkyl radicals.

3. As compositions of matter, the secondary polynitro amines having the general formula: L

wherein A is a lower alkylene radical and 1s a alkyl radical. 4. As compositions of matter, the secondary polynitro amines having the general formula:

lower wherein Ais a lower alkylene radical and R is a lower alkyl radical.

5. As a composition of matter, N-2,2,2-trinitroethyl- N-3-3-dinitrobutyl amine having the structural formula:

6. As a composition of matter, N-2,2-dinitropropyl- N-3,3,3-trinitropropyl amine having the structural 8. As a composition of matter, bis(2,2-dinitrobutyl) amine having the structural formula:

, 9. As a composition of matter, bis(2,2-dinitropentyl) amine having the structural formula:

' No, N0;

10. The method of preparing secondary amines having the general formula:

t 1 Ro--oH,-NH-A--cR' 1 N02 NO:

wherein A is a lower alkylene radical and R and R are radicals selected from a group consisting oflower alkyl and nitro radicals, at least'one R being lower alkyl; which comprises condensing a fi-geminal polynitro aliphatic alcohol with a compound selected from the group consisting of ammonia and aliphatic polynitro amines having the general formula: i

, 1\|TO2; RC A--NH wherein A and R are as defined above.

11. The method of claim 10 wherein the reaction is conducted at a pH below about 8.

12. The method of preparing secondary polynitro amineshaving the general formula: V

polynitro which comprises condensing an alcohol having the gen- ,eralformulafi. v @v RCCH2OH NO: I

with a'strong mineral acid salt of an amine having the general formula: i

N021 wherein A is a lower alkylene radical'and R and R" are 'radicals selected from a group consisting oflower alkyl and nitro radicals, at least one R being lower alkyl, in

which comprises condensing an alcohol having the gener-al formula:

R' I CH:0H N 1 with a strong mineral acid salt of an amine having the general formula:

N R'- :A-Nm

NO wherein A is a lower alkylene radical, R is a nitro radical and R is a lower alkyl radical; in the presence of a base selected from the group consisting of the hydroxides of alkali and alkaline earth metals.

14. The method of preparing secondary polynitro amines having the general formula:

which comprises condensing an alcohol having the general formula:

with a strong mineral acid salt of an amine having the general formula:

wherein A is a lower alkylene radical, R is a lower alkyl radical and R' is a nitro radical; in the presence of a base selected from the group consisting of the hydroxides of alkali and alkaline earth metals.

15. The method of preparing symmetrical aliphatic polynitro amines having the general formula:

which comprises condensing fl-geminal dinitro alcohols having the general formula:

wherein R is a lower alkyl radical, with ammonia.

16. The method of preparing N-2,2,2-trinitroethyl-N- 3,3-dinitrobutyl amine which comprises condensing 2,2,2- trinitroethanol with 3,3-dinitrobutyl amine hydrochloride in the presence of sodium hydroxide.

17. The method of preparing N-3,3-dinitropropyl-N- 3,3,3-trinitropropyl amine which comprises condensing 2,2-dinitropropanol with 3,3,3-trinitropropyl amine hydrochloride in the presence of sodium hydroxide.

18. The method of preparing bis(2,2-dinitropropyl) amine which comprises condensing 2,2-dinitropropanol in the presence of ammonia.

19. The method of preparing bis(2,2-dinitrobutyl) amine which comprises condensing 2,2-dinitrobutano1 in the presence of ammonia.

20. The method of preparing bis(2,2-dinitropentyl) amine which comprises condensing 2,2-dinitropentanol in the presence of ammonia.

References Cited in the file of this patent UNITED STATES PATENTS Schenck et al. Jan. 17, 1956 OTHER REFERENCES 

1. AS COMPOSITIONS OF MATTER, THE SECONDARY POLYNITRO AMINES HAVING THE GENERAL FORMULA: 